TY - JOUR
T1 - Comparing GIPAW with numerically exact chemical shieldings
T2 - The role of two-center contributions to the induced current
AU - de Wijs, Gilles A.
AU - Kresse, Georg
AU - Havenith, Remco W. A.
AU - Marsman, Martijn
N1 - Publisher Copyright:
© 2021 Author(s).
PY - 2021/12/21
Y1 - 2021/12/21
N2 - In this study, we benchmark density functional theory gauge-including projector-augmented-wave (GIPAW) chemical shieldings against molecular shieldings for which basis set completeness has been achieved [Jensen et al., Phys. Chem. Chem. Phys. 18, 21145 (2016)]. We demonstrate the importance of two-center corrections for GIPAW hydrogen shieldings. For the other nuclei studied, standard GIPAW is sufficiently accurate. We find that GIPAW can be pushed to closely approach the basis set limit. The only source of small inaccuracies lies in the contribution to the shielding that is caused by surface currents, which we estimate comparing GIPAW susceptibilities to converged molecular magnetizabilities.
AB - In this study, we benchmark density functional theory gauge-including projector-augmented-wave (GIPAW) chemical shieldings against molecular shieldings for which basis set completeness has been achieved [Jensen et al., Phys. Chem. Chem. Phys. 18, 21145 (2016)]. We demonstrate the importance of two-center corrections for GIPAW hydrogen shieldings. For the other nuclei studied, standard GIPAW is sufficiently accurate. We find that GIPAW can be pushed to closely approach the basis set limit. The only source of small inaccuracies lies in the contribution to the shielding that is caused by surface currents, which we estimate comparing GIPAW susceptibilities to converged molecular magnetizabilities.
UR - http://www.scopus.com/inward/record.url?scp=85122001737&partnerID=8YFLogxK
U2 - 10.1063/5.0069637
DO - 10.1063/5.0069637
M3 - Article
C2 - 34937373
AN - SCOPUS:85122001737
SN - 0021-9606
VL - 155
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 23
M1 - 234101
ER -